Synthesis of N ‐[1‐(2‐Hydroxyethyl)‐1 H ‐tetrazol‐5‐yl]‐ N ‐methylhydrazine as Polymeric Precursor

A nitrogen‐rich polymer was formed from the reaction of hexamethylene diisocyanate and N ‐[1‐(2‐hydroxyethyl)‐1 H ‐tetrazol‐5‐yl]‐ N ‐methylhydrazine ( 3 ) monomers. Compound 3 was synthesized by a nucleophilic substitution of the methylated sulfur atom of 4‐[2‐(acetoxy)ethyl]‐2‐methylthiosemicarbazide ( 10 ) with sodium azide and final deprotection of the formed N ‐[1‐2‐(acetoxyethyl)‐1 H ‐tetrazol‐5‐yl]‐ N ‐methylhydrazine ( 13 ). Moreover, the isomer 4‐(2‐azidoethyl)‐2‐methylsemicarbazide ( 18 ) to 3 was synthesized. Compounds 3 , 10 , 13 and 4‐[2‐(trimethylsilyloxy)ethyl]‐2‐methylthiosemicarbazide ( 15 ) were characterized by using vibrational spectroscopy (IR, Raman), mass spectrometry and multinuclear NMR spectroscopy. The crystal structures of 3 , 10 and 13 were determined by using single‐crystal X‐ray diffraction. The molecular weights of the polymers were determined by GPC. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)